US5411558A - Heavy oil emulsion fuel and process for production thereof - Google Patents
Heavy oil emulsion fuel and process for production thereof Download PDFInfo
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- US5411558A US5411558A US08/112,146 US11214693A US5411558A US 5411558 A US5411558 A US 5411558A US 11214693 A US11214693 A US 11214693A US 5411558 A US5411558 A US 5411558A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/32—Liquid carbonaceous fuels consisting of coal-oil suspensions or aqueous emulsions or oil emulsions
- C10L1/328—Oil emulsions containing water or any other hydrophilic phase
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
- Y10S516/924—Significant dispersive or manipulative operation or step in making or stabilizing colloid system
- Y10S516/927—Significant dispersive or manipulative operation or step in making or stabilizing colloid system in situ formation of a colloid system making or stabilizing agent which chemical reaction
Definitions
- the present invention relates to a heavy oil emulsion fuel of an oil-in-water type. More particularly, the present invention is concerned with an aqueous emulsion composition of a heavy oil having a particular particle size distribution and having a high heavy oil concentration, a low viscosity and an excellent storage stability and an aqueous emulsion composition of a heavy oil comprising a fatty acid distillation bottom or an edible oil, having an excellent storage stability and being nonpollutive.
- the present invention relates to a process for producing the heavy oil emulsion fuel described above.
- these heavy oils are usually an oleaginous material containing about 60 to 70% or, in some cases, 70% or more of a heavy faction having a boiling point of 420° to 450° C. or, in some cases, 450° C. or above, which is usually a vacuum distillation residue.
- they do not flow, or have a viscosity as high as tens of thousands of centipoises or more.
- a temperature as high as 280° to 300° C. not only do problems occur in handling, atomization, etc., but also problems of clogging the piping, etc., of boilers renders them very difficult to use.
- waste oil discharged from fast-food shops and confectioneries which are waste oils derived from edible oils, and which are believed to be used in an amount of several million tons a year in recent years all over the country, have come to be recovered as a recovered oil.
- further improvements in the recovery of the waste oil are expected.
- the development of useful applications of the recovered oil has not been made, so that the development of applications of the recovered oil from the viewpoint of the utilization of resources, has been desired in the art.
- the particle size distribution of the oil phase comprising a heavy oil is a very important factor and there exists an optimal particle size distribution for use of a heavy oil as an emulsion fuel, which has led to the completion of an oil-in-water type heavy oil emulsion fuel that has a viscosity relatively close to that of water, can be sufficiently atomized at a temperature of room temperature to 90° C., is excellent in handleability and fluidity despite a very high heavy oil concentration, and has a very excellent stability, such that neither sedimentation nor an increase in the viscosity occurs, even after storage for a long period of time.
- the present invention relates to an oil-in-water type heavy oil emulsion fuel comprising (a) a heavy oil, (b) a surfactant and (c) water, wherein oil particles having a diameter of 100 ⁇ m or less account for 80% by weight or more of all the oil particles and the oil particles have a particle size distribution such that the distribution constant, n, determined from two relational expressions obtained by substituting a particle diameter ( ⁇ m) corresponding to a cumulative oversize weight of 10% and a particle diameter ( ⁇ m) corresponding to a cumulative oversize weight of 90% for a Rosin-Rammler distribution function expressed by the equation (1) is in the range of from 0.5 to 1.6:
- R represents a cumulative oversize weight in %
- D represents a particle diameter
- n represents a constant (a distribution constant)
- D c represents a constant (a particle size characteristic constant).
- the present invention is an oil-in-water emulsion fuel comprising three components of (a) a heavy oil, (b) a surfactant and (c) water, characterized in that oil particles of component (a) having a diameter of 100 ⁇ m or less account for 80% by weight or more and, in a Rosin-Rammler distribution function expressed by the equation (1), the oil particles have a particle size distribution such that the distribution constant, n, determined from two points of a particle diameter ( ⁇ m) corresponding to a cumulative oversize weight of 10% and a particle diameter ( ⁇ m) corresponding to a cumulative oversize weight of 90% is in the range of from 0.5 to 1.6:
- R represents a cumulative oversize weight in %
- D represents a particle diameter
- n represents a constant (a distribution constant)
- D c represents a constant (a particle size characteristic constant).
- an oil-in-water type heavy oil emulsion fuel comprising a heavy oil, water and a fatty acid distillation bottom and/or a product obtained by reacting a fatty acid distillation bottom with a neutralizing agent or saponifier has a viscosity relatively close to that of water, can be sufficiently atomized at a temperature of room temperature to 90° C. is excellent in handleability and, by virtue of the effect of incorporation of the fatty acid distillation bottom or the product described above, is excellent in fluidity despite a very high concentration, and has such an excellent stability that neither sedimentation nor increase in the viscosity occurs even after storage for a long period of time.
- the present invention relates to an oil-in-water type heavy oil emulsion fuel comprising (a) a heavy oil, (c) water and (e-1) a fatty acid distillation bottom, and an oil-in-water type heavy oil emulsion fuel comprising (a) a heavy oil, (c) water and (b-1-1) a product obtained by reacting (e-1) a fatty acid distillation bottom with (f) a neutralizing agent or saponifier.
- the present inventors have made extensive studies and, as a result, have developed a fuel which serves as a substitute for fuel oil and is composed mainly of a heavy oil, which has been desired to be utilized as a new fossil fuel, and an edible oil.
- the present invention relates to an oil-in-water type heavy oil emulsion fuel comprising (a) a heavy oil, (c) water and (e-2) an edible oil, and an oil-in-water type heavy oil emulsion fuel comprising (a) a heavy oil, (c) water and (b-1-2) a product obtained by reacting (e-2) an edible oil with (f) a neutralizing agent or saponifier.
- a heavy oil can be emulsified and dispersed, without using any surfactant, by the use of a precursor of a particular emulsifier comprising a compound having a carboxyl group in its molecule or a precursor of the emulsifier comprising an ester and a neutralizing agent or a saponifier for the precursor.
- the present inventors have completed a process for producing an oil-in-water type heavy oil emulsion fuel which is excellent in fluidity despite a very high heavy oil concentration by virtue of a particular particle size distribution of its oil phase and has such an excellent stability that neither sedimentation nor increase in the viscosity occurs, even after storage for a long period of time.
- the present invention relates to a process for producing an oil-in-water type heavy oil emulsion fuel which comprises producing an emulsion from 60 to 85% by weight of (a) a heavy oil, 10 to 40% by weight of (c) water, 0.01 to 10% by weight of (e) a precursor of an emulsifier comprising a compound having a carboxyl group in its molecule or an ester, and 0.01 to 5% by weight of (f) a neutralizing agent or saponifier for the precursor (e) while reacting the precursor (e) with the neutralizing agent or saponifier (f) to form an emulsifier.
- the present invention relates to a process for producing an oil-in-water type heavy oil emulsion fuel in which oil particles having a diameter of 100 ⁇ m or less account for 80% by weight or more of all the oil particles in the emulsion and the oil particles in the emulsion have a particle size distribution such that the distribution constant, n, determined from two relational expressions obtained by substituting a particle diameter ( ⁇ m) corresponding to a cumulative oversize weight of 10% and a particle diameter ( ⁇ m) corresponding to a cumulative oversize weight of 90% for a Rosin-Rammler distribution function expressed by the equation (1) is in the range of from 0.5 to 1.8:
- R.sub.(D) represents a cumulative oversize weight in %
- D represents a particle diameter
- n represents a constant (a distribution constant)
- De represents a constant (a particle size characteristic constant).
- the "heavy oil” to be used as component (a) in the present invention includes the following oils which do not flow unless they are heated to high temperature, since they have poor flowability at ordinary temperatures.
- Petroleum-derived asphalt and a mixture containing the asphalt.
- heavy oil those containing components having a boiling point of 340° C. or above under atmospheric pressure in an amount of 90% by weight or more are preferable.
- the surfactant to be used as component (b) in the present invention includes nonionic surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants.
- examples of the surfactants include the following.
- alkylene oxide adduct of a compound having a phenolic hydroxyl group such as phenol, cresol, butylphenol, nonylphenol, dinonylphenol, dodecylphenol, p-cumylphenol or bisphenol A, wherein the alkylene oxide is ethylene oxide, ethylene oxide/propylene oxide, ethylene oxide/butylene oxide or ethylene oxide/styrene oxide.
- An alkylene oxide adduct of a formaldehyde condensate of a compound having a phenolic hydroxyl group such as an alkylphenol, phenol, m-cresol, styrenated phenol or benzylated phenol, wherein the average degree of condensation is 1.2 to 100, preferably 2 to 20, and the alkylene oxide is ethylene oxide, ethylene oxide/propylene oxide, ethylene oxide/butylene oxide or ethylene oxide/styrene oxide.
- alkylene oxide adduct of a monohydric aliphatic alcohol and/or an aliphatic amine having 2 to 50 carbon atoms wherein the alkylene oxide is ethylene oxide, ethylene oxide/propylene oxide, ethylene oxide/butylene oxide or ethylene oxide/styrene oxide.
- An alkylene oxide adduct of a polyhydric alcohol such as glycerol, trimethylolpropane, pentaerythritol, sorbitol, sucrose, polyglycerol, ethylene glycol, polyethylene glycol, propylene glycol or polypropylene glycol, or an ester of the above-described polyhydric alcohol with a fatty acid having 8 to 18 carbon atoms, wherein the alkylene oxide is ethylene oxide, ethylene oxide/propylene oxide, ethylene oxide/butylene oxide or ethylene oxide/styrene oxide.
- a polyhydric alcohol such as glycerol, trimethylolpropane, pentaerythritol, sorbitol, sucrose, polyglycerol, ethylene glycol, polyethylene glycol, propylene glycol or polypropylene glycol, or an ester of the above-described polyhydric alcohol with a fatty acid having 8 to 18 carbon atoms, wherein the
- An alkylene oxide adduct of a polyamine having a plurality of active hydrogen atoms such as ethylenediamine, tetraethylenediamine or polyethyleneimine (molecular weight: 600 to 10,000), wherein the alkylene oxide is ethylene oxide, ethylene oxide/propylene oxide, ethylene oxide/butylene oxide or ethylene oxide/styrene oxide.
- nonionic surfactants include those belonging to groups (i), (ii), (iii) and (iv) described above.
- a sulfonic acid of an aromatic ring compound such as naphthalene, alkylnaphthalene, alkylphenol and alkylbenzene or a salt thereof, or a formalin (or a formaldehyde) condensate of a sulfonic acid of an aromatic ring compound or a salt thereof, wherein the average degree of condensation of formalin is 1.2 to 100 and the salt is an ammonium salt, a lower amine salt such as a monoethanolamine, diethanolamine, triethanolamine or triethylamine salt, or an alkali metal or alkaline earth metal salt such as a sodium, potassium, magnesium or calcium salt.
- a lower amine salt such as a monoethanolamine, diethanolamine, triethanolamine or triethylamine salt
- an alkali metal or alkaline earth metal salt such as a sodium, potassium, calcium or magnesium salt.
- a lower amine salt such as a monoethanolamine, diethanolamine, triethanolamine or triethylamine salt
- an alkali metal or alkaline earth metal salt such as a sodium, potassium, calcium or magnesium salt.
- (V) A copolymer of maleic anhydride or/and itaconic anhydride with other comonomer(s), or a salt thereof, wherein the molecular weight is 500 to 500,000, and the salt is an ammonium salt or an alkali metal salt such as a sodium or potassium salt.
- a maleinized liquid polybutadiene or a salt thereof wherein the molecular weight of the liquid polybutadiene as the starting material is 500 to 200,000, and the salt is an ammonium salt or an alkali metal salt, such as a sodium or potassium salt.
- a sulfuric ester salt of an alcohol having 4 to 18 carbon atoms wherein the salt is an ammonium salt, a lower amine salt such as a monoethanolamine, diethanolamine, triethanolamine or triethylamine salt, or an alkali metal or alkaline earth metal salt such as a sodium, potassium, magnesium or calcium salt;
- alkyldiphenyletherdisulfonic acid or a salt thereof wherein the alkyl group has 8 to 18 carbon atoms, and the salt is an ammonium, sodium, potassium, magnesium or calcium salt;
- a rosin or a rosin acid or a resin acid
- the salt is an ammonium, sodium or potassium salt, which includes, for example, a mixed tall acid comprising a tall rosin and a tall oil fatty acid, i.e., a higher fatty acid, a tall rosin, a gum rosin, a wood rosin and salts thereof;
- an ⁇ -sulfofatty acid ester salt represented by the following general formula: ##STR1## wherein R 1 represents an alkyl- or alkenylgroup having 6 to 22 carbon atoms, R 2 represents an alkyl group having 1 to 22 carbon atoms, M represents an alkali metal ion, an alkaline earth metal ion, an ammonium ion or an organic amine, and n is 1 or 2.
- anionic surfactants include those belonging to groups (I), (II), (III), (IV) and (VII) described above.
- XII A quaternary ammonium salt represented by the following formulae (1), (2) or (3): ##STR2## wherein R 1 , R 2 , R 3 and R 4 represent each an alkyl or alkenyl group having 1 to 18 carbon atoms and X.sup. ⁇ represents a counter anion, e.g., a chlorine ion and a bromine ion, wherein R 1 , R 2 , R 3 and X.sup. ⁇ are as defined above, and ##STR3## wherein R 5 represents an alkyl or alkenyl group having 8 to 18 carbon atoms, R 6 represents a hydrogen atom or a methyl group and X.sup. ⁇ is as defined above.
- R is as defined above and X' represents an inorganic or organic acid, e.g., hydrochloric acid and acetic acid.
- cationic surfactants include those belonging to groups (XI), (XII), (XVI) and (XVII) described above.
- the surfactant (b) includes a soap such as (b-1) a product obtained by reacting (e) a precursor with (f) a neutralizing agent or saponifier. Therefore, surfactants other than the product (b-1) are called component (b-2) in the present invention.
- the precursor of an emulsifier as component (e) in the present invention is a compound having a carboxyl group in its molecule or an ester.
- the compound having a carboxyl group in its molecule is preferably at least one member selected from the group consisting of a chain monocarboxylic acid, a cyclic saturated fatty acid and a diterpenoid carboxylic acid.
- the ester as the precursor of the emulsifier includes triglycerides and examples thereof include an ester which can be decomposed into a compound having a carboxyl group in its molecule.
- the ester is preferably a natural fat or oil.
- preferred examples of the chain monocarboxylic acid include caprylic, captic, lauric, myristic, palmitic, stearic, behenic, oleic and linoleic acids
- preferred examples of the cyclic saturated fatty acid include petroleum and naphthenic acids
- preferred examples of the diterpenoid carboxylic acid include resin acid, rosin and abletic acid
- preferred examples of the natural fat and oil include coconut oil, palm kernel oil, babassu kernel oil, castor oil, linseed oil, lard, beef tallow, fish oil and tall oil.
- the precursor of the emulsifier is not limited to the abovedescribed specific examples only.
- a fatty acid distillation bottom (e-1) and an edible fat and oil (e-2) are also one of the precursors (e).
- the "fatty acid distillation bottom" as component (e-1) refers to a by-product generated in the production of fatty acids by using beef tallow, coconut oil, palm oil or the like as the raw material and is a “residuum” in the distillation according to the following general production process:
- the fatty acid distillation bottom contains many impurities and is poor in odor and hue, it has no value in use, so that it is currently disposed of as industrial wastes.
- the composition of the fatty acid distillation bottom varies depending upon the kind of raw material and the production process and, hence, is not particularly limited.
- the distillation bottom has an approximate composition comprising 10 to 90% by weight of a fatty acid, 90 to 10% by weight of a fatty acid ester and other impurities such as resinous substances, inorganic substances and metals.
- the edible oil (e-2) to be used in the present invention may have the same composition as that of commercially available general edible oils. Although these fats and oils comprise various fatty acids, the content of C 18 (Cn: carbon atom number of the fatty acid) fatty acids is high and other constituent fatty acids include C 12 , C 14 , C 16 , C 20 , C 22 , and C 24 , fatty acids. In the present invention, among the edible oils, the recovered oil of edible fats and oils is preferably used from the viewpoint of the problem of resource and environment.
- the "recovered oil of the edible fat and oil” is intended to mean recovered oils of used edible fats and oils, such as soybean oil, rapeseed oil and corn oil, that are discharged in a large amount from fast-food shops, confectioneries and the general household and have not been effectively used due to their odor and color.
- the acid value of the edible oil is generally 1 or less
- the recovered oil exhibits an acid value as large as 1 to 30 due to the progress of rancidillcation.
- the recovered oil has a saponification value of about 50 to 250 and an iodine value of about 10 to 150. These properties often somewhat change as compared with those before use.
- the neutralizing agent or saponifier as component (f) includes, for example, a hydroxide of an alkali metal, ammonia and an amine. Preferred examples thereof include a baslc compound (f-1) such as KOH. These compounds react with the fatty acids in the fatty acid distillation bottom or the edible oil to form a soap. Namely, these compounds serve as a neutralizing agent and a saponifier. Therefore, component (f) is called as a neutralizing agent or saponifier in the present invention.
- the soap produced serves as a surfactant.
- Water as component (c) includes city water, deionized water and so on.
- the water-soluble polymer as component (d) and the polyhydric alcohol as component (g) are stabilizers for an emulsion.
- the water-soluble polymer includes water-soluble synthetic polymers and water-soluble polymers derived from naturally occurring matter (including microorganisms). It is preferred to use the water-soluble synthetic polymers in the present invention. Specific examples of the water-soluble polymer are as follows:
- (c) A homopolymer of maleic anhydride or iraconic anhydride, or a copolymer thereof represented by the following formula: ##STR14## wherein M 2 represents a maleic anhydride or itaconic anhydride residue; Z 3 represents an ⁇ -olefin (ethylene, propylene, butylene, isobutylene, octene, decene, dodecene or the like) or styrene residue; and n is 50 to 100,000.
- Z 5 represents a divalent group derived from a comonomer copolymerizable with vinylpyrrolidone or a salt (NH 4 , Na, K or Li) thereof, for example, acrylamide, vinylsulfonic acid, methallylsulfonic acid, maleic anhydride, iraconic anhydride or a salt (NH 4 , Na, K or Li) thereof, styrene, ⁇ -olefin (C 2-18 ) or the like; and n is 50 to 100,000.
- water-soluble synthetic polymers include those belonging to groups (a), (b), (d) and (f) described above.
- Preferable examples of the water-soluble polymers derived from naturally occurring matter include those belonging to groups (A), (B)-(b), (B)-(c) and (D) described above.
- the polyhydric alcohol as component (g) is those having two or more of hydroxyl groups in its molecule and being soluble in water, and examples thereof include monosaccharides and polysaccharides, such as glycerol, polyglycerol, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, oligosaccharide, sorbitol and glucose.
- the present invention provides an oil-in-water type heavy oil emulsion fuel comprising three components of (a) a heavy oil, (b) a surfactant and (c) water, wherein oil particles having a diameter of 100 ⁇ m or less account for 80% by weight or more of all the oil particles and the oil particles have a particle size distribution such that the distribution constant, n, determined from two relational expressions obtained by substituting a particle diameter ( ⁇ m) corresponding to a cumulative oversize weight of 10% and a particle diameter ( ⁇ m) corresponding to a cumulative oversize weight of 90% for a Rosin-Rammler distribution function expressed by the equation (1) is in the range of from 0.5 to 1.6:
- R represents a cumulative oversize weight in %
- D represents a particle diameter
- n represents a constant (a distribution constant)
- D c represents a constant (a particle size characteristic constant).
- An emulsion comprising two liquids insoluble in each other, one of which is dispersed in a fine particle form in the other liquid, gives a thermodynamically unstable nonequilibrium system because the free energy of the interface of the two liquids increases with an increase in the area of the interface of the two liquids, so that the state of dispersion varies with time and the emulsion form is gradually broken.
- the present inventors have noted the physicochemical properties of the system and thought that, in order to increase the concentration of the emulsion, i.e., the concentration of the oil phase, it is necessary to minimize the proportion of gaps between particles (porosity) for enabling a heavy oil to be utilized or filled at a high density, thereby minimizing the amount of a solvent (water) necessary for fluidizing the emulsion and, further, in order to stabilize the system, it is necessary to minimize the increase in the area of interface of the heavy oil, i.e., the oil phase, and water to lower the free energy at the interface. Based on this concept, the present inventors have focused on the particle size distribution of the oil phase.
- the oil particles that is, the oil droplets or the internal phases, have a particle size distribution such that the distribution constant, n, determined from two relational expressions obtained by substituting a particle diameter ( ⁇ m) corresponding to a cumulative oversize weight of 10% and a particle diameter ( ⁇ m) corresponding to a cumulative oversize weight of 90% for a Rosin-Rammler distribution function expressed by the equation (1) is in the range of from 0.5 to 1.6, preferably in the range of from 0.7 to 1.4, still preferably in the range of from 0.8 to 1.3.
- this value is smaller than 0.5, that is, the grain size distribution is broader, it becomes difficult to produce an emulsion and, at the same time, there occurs an increase in the proportion of the gap between the particles, which makes an increase in the concentration of the emulsion difficult.
- the oil particles comprising the heavy oil have an average particle size preferably in the range of from 3 to 50 ⁇ m, still preferably in the range of from 3 to 30 ⁇ m, particularly preferably in the range of from 3. to 20 ⁇ m, and further should have a particle size distribution such that particles having a diameter of 100 ⁇ m or less account for 80% by weight or more of all the oil particles and, preferably, particles having a diameter of 1 ⁇ m or less is 15% by weight or less of all the oil particles.
- the emulsion does not burn very well when it is used as a fuel, which lowers the combustion efficiency and causes precipitation to occur during storage or the clogging of piping, etc., of boilers.
- the resultant emulsion does not satisfy the above-described particle size distribution requirements and has a relatively narrow particle size distribution having a distribution constant, n, of about 1.8.
- a heavy oil emulsion fuel having such a particle size distribution cannot provide an emulsion fuel having high concentration, low viscosity and excellent storage stability as contemplated by the present invention.
- the particle size distribution was measured with a laser beam diffraction/scattering particle size distribution measuring device (LA700 manufactured by Horiba, Ltd.).
- a specially devised particle size regulation method rather than simple emulsification.
- the method include one which comprises using a plurality of emulsifiers in parallel and operating the emulsifiers with shear forces different from each other to produce emulsions different from each other in particle size distribution and mixing these emulsions to attain an optimal particle size distribution.
- Another method comprises varying the kind and amount of addition of the surfactant to produce emulsions different from each other in particle size distribution and mixing the emulsions to attain an optimal particle size distribution.
- Still another method comprises continuously producing an emulsion on a line mixer or the like, while circulating part of the emulsion, while regulating the amount and time of circulation, thereby providing an emulsion having a broad particle size distribution.
- An additional method comprises continuously producing an emulsion on a line mixer or the like while periodically varying the kind and/or amount of feed of the surfactant while regulating the cycle time according to the kind and/or amount of feed of the surfactant to provide an emulsion having a broad particle size distribution.
- Emulsifiers or dispersing devices commonly used in the art such as a homomixer, a homogenizer, a line mixer, a colloid mill, a sand mill, a milder, a static mixer and a motionless mixer, may be used as the emulsifier in the present invention.
- the concentration of the heavy oil used as component (a) of tile emulsion fuel in the present invention is preferably in the range of from 60 to 85% by weight, still preferably in the range of from 65 to 80% by weight, particularly preferably in the range of from 70 to 75% by weight.
- the concentration is excessively low, the calorific power is lowered and, in some cases, it becomes difficult to conduct direct combustion.
- the concentration is excessively high, the viscosity of the emulsion becomes so high that the fluidity is lowered and, at the same time, coalescence or agglomeration of the particles occurs during storage which causes a deterioration in its storage stability.
- the surfactant as component (b) is at least one member selected from among nonionic, anionic, cationic and amphoteric surfactants.
- the amount of use of the surfactant (b) is preferably in the range of from 0.01 to 5% by weight, still preferably in the range of from 0.05 to 3.0% by weight, particularly preferably in the range of from 0.1 to 1.0% by weight in the emulsion fuel, i.e., based on the entire amount of the emulsion fuel.
- the amount is below the above-described range, the emulsification of the heavy oil and the development of the emulsification stability are unsatisfactory.
- the amount is above the above-described range, the profitability is low and, further, foaming occurs during emulsification or the regulation of the particle diameter becomes difficult.
- the amount of introduced water as component (c) is important, and it is preferably 10 to 40% by weight, still preferably 15 to 35% by weight, particularly preferably 20 to 30% by weight.
- the amount of water is below the above-described range, no improvement in the emulsification stability can be attained and only an emulsion having a poor fluidity is provided even though the particle size distribution of the oil phase is optimized or the kind and/or amount of use of the surfactant as component (b) is optimized.
- the amount of water is above the above-described range, the calorific power as a fuel becomes so low that direct combustion becomes difficult. Therefore, the use of water in an amount outside the above-described range should be avoided.
- a water-soluble polymer as a component (d).
- a water-soluble polymer having a molecular weight of 10,000 or more can be incorporated in an amount of preferably 0.005 to 3 parts by weight, still preferably 0.008 to 2 parts by weight, particularly preferably 0.01 to 1 part by weight based on 100 parts by weight of the entire amount of the components (a), (b) and (c) for the purpose of further improving the storage stability.
- the surfactant (b) is not an essential component.
- a precursor (e) of an emulsifier and a neutralizing agent or saponifier (f) can be used instead of the surfactant (b), and the precursor (e) is reacted with the neutralizing agent or saponifier (f) during emulsification to form a soap, that is surfactant (b).
- the present invention also provides a process for producing an oil-in-water type heavy oil emulsion fuel which comprises producing an emulsion from 60 to 85% by weight, preferably 65 to 80% by weight, still preferably 70 to 75 by weight of a heavy oil (a), 10 to 40% by weight, preferably 15 to 35% by weight, still preferably 20 to 30 by weight of water (c), 0.01 to 10% by weight, preferably 0.05 to 5% by weight, still preferably 0.1 to 1.0 by weight of a precursor (e) of an emulsifier comprising a compound having a carboxyl group in its molecule or an ester, and 0.01 to 5% by weight of a neutralizing agent or saponifier (f) for the precursor (e), while reacting the precursor (e) with the neutralizing agent or saponifier (f) to form an emulsifier.
- a precursor (e) of an emulsifier comprising a compound having a carboxyl group in its molecule or an ester
- the emulsion to be obtained preferably has such properties that oil particles having a diameter of 100 ⁇ m or less account for 80% by weight or more of all the oil particles in the emulsion and the oil particles in the emulsion have a particle size distribution such that the distribution constant, n, determined from two relational expressions obtained by substituting a particle diameter ( ⁇ m) corresponding to a cumulative oversize weight of 10% and a particle diameter ( ⁇ m) corresponding to a cumulative oversize weight of 90% for a Rosin-Rammler distribution function expressed by the equation (1) described above is in the range of from 0.5 to 1.8, preferably in the range of from 0.5 to 1.6, still preferably in the range of from 0.7 to 1.6, particularly preferably in the range of from 0.8 to 1.5. That is, the above-described process is preferably conducted to produce an emulsion having the above-described properties.
- a heavy oil emulsion fuel having such a broad particle size distribution that the distribution constant, n, is 1.8 or less can be produced by using a precursor (e) of a particular emulsifier comprising a compound having a carboxyl group in its molecule or a precursor (e) of the emulsifier comprising an ester and a neutralizing agent or saponifier (f) for the precursor and causing the heavy oil (a) to be emulsified and dispersed while reacting the precursor (e) with the neutralizing agent or saponifying agent (f) at a temperature in the range of from 80° to 200° C. to form an emulsifier, i.e., a soap.
- the emulsion fuel having the broad particle size distribution of the present invention is formed through the following mechanism.
- the particle diameter of the oil particles of the emulsion depends upon the concentration of the surfactant, that is, the interfacial tension of the system. Specifically, when the concentration of the surfactant is low, the interfacial tension is so high that the particle diameter of the oil particles is large. On the other hand, when the concentration of the surfactant is high, the interfacial tension is so low that the particle diameter of the oil particles becomes small.
- the precursor of the surfactant reacts with the neutralizing agent during the emulsification to gradually release the surfactant into the system.
- the concentration of the surfactant in the system gradually increases from zero and continues to increase until the reaction of the precursor with the neutralizing agent is completed.
- the interfacial tension of the system increases with time, which causes an emulsion having a broad particle size distribution, that is, containing oil particles having a wide range of particle diameters from a large particle diameter to a small particle diameter.
- additives i.e., the precursor (e) and the neutralizing agent or saponifier (f)
- the precursor (e) and the neutralizing agent or saponifier (f) in the same manner as that used in the nascent soap method known in the art, that is, a method wherein a precursor (e) comprising a compound having a carboxyl group in its molecule or a precursor (e) comprising an ester is dissolved in the heavy oil (a) while the neutralizing agent or saponifier (f) is dissolved in water (c).
- An emulsion wherein a soap is formed at the interface can be prodnced by mixing the two phases. What is particularly important in the present invention is that the surfactant should be gradually released into the system during the emulsification.
- the control of release of the surfactant is important.
- Factors for controlling the release of the surfactant include the reaction temperature, the reaction time, the shearing force in agitation for mixing and the reaction rate constant of the precursor.
- a heavy oil emulsion fuel having an intended broad distribution can be provided by controlling these factors.
- the method for adding additives is not limited to the above-described method.
- the precursor (e) comprising a compound having a carboxyl group in its molecule or the precursor (e) comprising an ester may be dispersed in water.
- the neutralizing agent or saponifier may be dissolved in the heavy oil. What is important is to form such a system that the precursor (e) comprising a compound having a carboxyl group in its molecule or the precursor (e) comprising an ester and the neutralizing agent or saponifier (f) coexist during the emulsification of water (c) and the heavy oil (a) to bring about a reaction for forming an emulsifier.
- the precursor (e) and the neutralizing agent or saponifier (f) are as described above.
- the amount of the precursor (e) used is in the range from 0.01 to 10% by weight, preferably in the range of from 0.05 to 5% by weight, still preferably in the range of from 0.1 to 1.0% by weight in the emulsion fuel, i.e., based on the entire amount of the emulsion fuel.
- the amount of use is below the above-described range, the emulsification of the heavy oil (a) and the development of the emulsification stability are unsatisfactory.
- the use of the precursor (e) in an amount exceeding the above-described range not only is unfavorable from the viewpoint of profitability but also produces foaming during the emulsification and often makes it difficult to regulate particle diameter.
- the amount of use of the neutralizing agent or saponifier (f) is 0.01 to 5% by weight in the emulsion fuel, i.e., based on the entire amount of the emulsion fuel and preferably an amount necessary for neutralizing or saponifying the precursor (e) may be properly selected.
- surfactants i.e., surfactants (b-2) described above, may be used in combination with the above-descried components, i.e., the heavy oil (a), water (c), the precursor (e) and the neutralizing agent or saponifier (f).
- the combined use of the surfactant (b-2) can contribute to a further improvement in the emulsifiability and emulsion stability.
- At least one member selected from the group consisting of surfactants (b-2) can be used.
- the surfactant (b-2) may be a nonionic surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant or a mixture of two or more surfactants.
- the amount of use of the surfactant (b-2) is in the range of from 0.01 to 5% by weight, preferably in the range of from 0.05 to 3% by weight, still prferably in the range of from 0.1 to 1.0% by weight base on the entire amount of the components (a), (c), (e) and (f).
- a water-soluble polymer described above as a component (d).
- a water-soluble polymer (d) having a molecular weight of 10,000 or more can be incorporated in an amount of 0.005 to 3 parts by weight, preferably 0.008 to 2 parts by weight, still preferably 0.01 to 0.5 part by weight based on 100 parts by weight of the entire amount of the components (a), (c), (e) and (f) for the purpose of further improving the storage stability.
- the present invention further provides an oil-in-water type heavy oil emulsion fuel comprising three components of (a) a heavy oil, (c) water and (e-1) a fatty acid distillation bottom.
- the oil-in-water type heavy oil emulsion fuel described above further comprises, besides the components (a), (c) and (e-1), a surfactant, other than (b-1), i.e., a product obtained by reacting (e) a precursor with (f) a neutralizing agent or saponifier, i.e., a surfactant (b-2).
- a surfactant other than (b-1)
- a neutralizing agent or saponifier i.e., a surfactant (b-2).
- the oil-in-water type heavy oil emulsion fuel described above comprises preferably 40 to 85% by weight, still preferably 50 to 80% by weight, particularly preferably 60 to 75% by weight of the heavy oil as component (a), preferably 0.1 to 5% by weight, still preferably 0.2 to 3% by weight, particularly preferably 0.3 to 2% by weight of the surfactant as component (b-2), preferably 10 to 40% by weight, still preferably 15 to 35% by weight, particularly preferably 15 to 25% by weight of water as component (c) and preferably 0.1 to 50% by weight, still preferably 0.2 to 40% by weight, particularly preferably 0.3 to 30% by weight of the fatty acid distillation bottom as component (e-1).
- the present inventors have noted the interface of water (c) and the heavy oil (a) and, as a result, have found a fatty acid distillation bottom (e-1) as a compound which is less liable to dissolve in both the water and heavy oil phases. It is conceivable that the fatty acid distillation bottom (e-1) is preferentially distributed in the interfacial phase, which reduces the free energy of the interface of the water phase and the heavy oil phase and serves to enhance the stability of the system.
- the amount of incorporation of the fatty acid distillation bottom (e-1) in the emulsion fuel is preferably in the range of from 0.1 to 50% by weight, still preferably in the range of from 0.2 to 40% by weight, particularly preferably in the range of from 0.3 to 30% by weight.
- the amount of incorporation is below this range, the effect of imparting long-term stability is poor and it is difficult to attain the effect of reducing the contents of the soot and dust and the nitrogen oxides present in the exhaust gases.
- this amount exceeds 50% by weight, the amount of inorganic substances and metals derived from the distillation bottom is increased, resulting in a composition unsuitable for use as a fuel.
- the concentration of the heavy oil as component (a) of the emulsion fuel described above is preferably in the range of from 40 to 85% by weight, still preferably in the range of from 50 to 80% by weight, particularly preferably in the range of from 60 to 75% by weight.
- concentration is excessively low, the calorific power is lowered and, in some cases, it becomes difficult to achieve direct combustion.
- concentration is excessively high, the viscosity of the emulsion fuel becomes so high that the fluidity is lowered and, at the same time, coalescence or agglomeration of the particles occurs during storage causing a deterioration in the storage stability.
- the surfactant as component (b-2) is at least one member selected from among nonionic, anionic, cationic and amphoteric surfactants.
- the amount of use of the surfactant (b-2) is preferably in the range of from 0.1 to 5% by weight, still preferably in the range of from 0.2 to 3.0% by weight, particularly preferably in the range of from 0.3 to 2.0% by weight in the emulsion fuel, i.e., based on the entire amount of the emulsion fuel.
- the amount is below the above-described range, the emulsification of the heavy oil and the development of the emulsification stability are unsatisfactory.
- the amount is above the above-described range, the profitability is low and, further, foaming occurs during emulsification or the regulation of the particle diameter becomes difficult.
- the amount of introduced water as component (c) is important, and it is preferably 10 to 40% by weight, still preferably 15 to 35% by weight, particularly preferably 15 to 25% by weight.
- the amount of water is below the above-described range, no improvement in the emulsification stability can be attained and only an emulsion fuel-having a poor fluidity is provided, even though the particle size distribution of the oil phase is optimized or the kind and/or amount of use of the surfactant as component (b) is optimized.
- the amount of water is above the above-described range, the calorific power as a fuel becomes so low that direct combustion becomes difficult. Therefore, the use of water in an amount outside the above-described range should be avoided.
- a water-soluble polymer (d) and/or a polyhydric alcohol (g) as a stabilizer.
- the water-soluble polymer (d) having a molecular weight of 10,000 or more can be incorporated in an amount of 0.005 to 3 parts by weight, preferably 0.008 to 2 parts by weight, particularly preferably 0.01 to 0.5 part by weight based on 100 parts by weight of the entire amount of the components (a), (b-2), (c) and (e-1) for the purpose of further improving the storage stability.
- the polyhydric alcohol (g) can be incorporated in an amount of 0.1 to 50 parts by weight, preferably 0.2 to 40 parts by weight, still preferably 0.3 to 30 parts by weight based on 100 parts by weight of the entire amount of the components (a), (b-2), (c) and (e-1) for the purpose of further improving the storage stability.
- the fatty acid distillation bottom (e-1) can be incorporated by a method wherein the heavy oil (a) and the distillation bottom (e-1) are heated and mixed with each other before the production of an emulsion or a method wherein the distillation bottom (e-1) is added during the production of an emulsion.
- the distillation bottom (e-1) since the distillation bottom (e-1) has a poor fluidity at room temperature, it is preferred to heat the distillation bottom (e-1) at 50° C. or above before the addition.
- the emulsion to which the distillation bottom (e-1) has been incorporated is acidic.
- a hydroxide of an alkali metal, ammonia and/or an amine are suitable as the neutralizing agent.
- the neutralizing agent may be dissolved in water before the production of the emulsion or alternatively may be added during the production of the emulsion.
- the amount of addition of the neutralizing agent is preferably such that the resultant emulsion is neutral or weakly alkaline.
- the neutralizing agent reacts with the distillation bottom (e-1) to form a soap.
- the neutralizing agent serves also as a saponifier. Therefore, the neutralizing agent is the neutralizing agent or saponifier (f) described above.
- the heavy oil emulsion fuel contains (b-1-1) a product obtained by reacting (e-1) a fatty acid distillation bottom with (f) a neutralizing agent or saponifier.
- the heavy oil emulsion fuel comprises components (a), (c), (e-1) and (b-1-1), or components (a), (c) and (b-1-1), depending on the amount of the neutralizing agent or saponifier (f).
- the mechanism for reduction of the contents of the soot and dust and the nitrogen oxides in the exhaust gases is not clear but it is thought as follows.
- Asphalts and bitumens as the heavy oil have higher residual carbon and nitrogen contents than those of gas oil, kerosine, fuel oil and other oils generally used as a fuel, so that when they are used as a fuel, an increase in the soot and dust and the nitrogen oxides is unavoidable.
- the calorific value in the combustion is substantially equal to that of the heavy oil, but no significant amount of residual carbon and nitrogen is present. Therefore, the fuel NOx derived from nitrogen contained in the soot and dust and the fuel decreases with an increasing proportion of incorporation of the fatty acid distillation bottom (e-1) relative to the heavy oil.
- the present invention provides an oil-in-water type heavy oil emulsion fuel comprising three components of (a) a heavy oil, (c) water and (e-2) an edible oil.
- the oil-in-water type heavy oil emulsion fuel described above further comprises, besides the components (a), (c) and (e-2), a surfactant other than (b-1) a product obtained by reacting (e) a precursor with (f) a neutralizing agent or saponifier, i.e., a surfactant (b-2).
- a surfactant other than (b-1) a product obtained by reacting (e) a precursor with (f) a neutralizing agent or saponifier, i.e., a surfactant (b-2).
- the oil-in-water type heavy oil emulsion fuel described above preferably has the components (a), (b2), (c) and (e-2) the following ratio. Namely, the ratio of the entire amount of the components (a) and (e-2) to the amount of the component (c) is 60 to 90: 40 to 10 by weight, preferably 65 to 85: 35 to 15 by weight, still preferably 70 to 80: 30 to 20 by weight and the amount of the component (b-2) is 0.1 to 5% by weight, preferably 0.2 to 3% by weight, still preferably 0.3 to 2% by weight based on the entire amount of the components (a), (c) and (e-2).
- the emulsion fuel described above has a viscosity relatively close to that of water, can be sufficiently atomized at a temperature of room temperature to 90° C. and is excellent in the handleability and, by virtue of the effect of incorporation of the edible oil (e-2), is further excellent in fluidity despite a very high heavy oil concentration, and has such an excellent stability that neither sedimentation nor increase in the viscosity occurs even after storage for a long period of time. Further, the emulsion fuel of the present invention is a nonpollutive fuel because the contents of the soot and dust and the nitrogen oxides in the exhaust gases are significantly reduced by virtue of the effect of incorporation of the edible oil (e-2).
- an emulsion comprising two liquids insoluble in each other one of which is dispersed in granular form in the other liquid gives a thermodynamically unstable nonequilibrium system because the free energy of the interface of the two liquids increases with an increase in the area of the interface of the two liquids, so that the state of dispersion varies with time toward demulsification.
- surfactants for the purpose of improving the stability of the system through a reduction in the free energy of the interface. No matter how high the performance of the surfactant is, the free energy of the interface cannot be reduced to zero, so that it is difficult to provide an emulsion which is truly stable.
- the present inventors have noted the interface of water (c) and the heavy oil (a) and assumed that the addition of an edible oil (e-2) causes fatty acid molecules contained in the edible oil (e-2) to be preferentially distributed to the interfacial phase, which reduces the free energy of the interface of the water and the heavy oil and serves to enhance the stability of the system.
- the weight ratio of the entire amount of the heavy oil (a) and the edible oil (e-2) to water (c) is in the range of from 60:40 to 90:10, preferably in the range of from 65:35 to 85:15, still preferably 70:30 to 80:20.
- the proportion of the oil is excessively low, the calorific power of the fuel is lowered and, at the same time, it often becomes difficult to effect direct combustion.
- the ratio of incorporation of the heavy oil (a) to this edible oil (e-2) is in the range of from 5:95 to 95:5, preferably in the range of from 20:80 to 80:20, still preferably in the range of from 30:70 to 70:30, from the viewpoint of combustibility.
- the proportion of the heavy oil (a) is high, the amounts of fuel NO x and the soot and dust attributable to the heavy oil is increased.
- the proportion of the edible oil (e-2) is high, the burning off of the fuel can be improved, but there occurs an increase in the thermal NO x attributable to a rise in the flame temperature.
- the amount of use of the surfactant (b-2) is preferably in the range of from 0.1 to 5 parts by weight, still preferably in the range of from 0.1 to 3 parts by weight, particularly preferably in the range of from 0.1 to 1.0 part by weight based on 100 parts by weight of the entire amount of the oil phase components and water, i.e., 100 parts by weight of the entire amount of the components (a), (c) and (e-2).
- the amount is below the above-described range, the emulsification of the heavy oil and the development of the emulsification stability are unsatisfactory.
- the amount is above the above-described range, the profitability is low and, further, foaming occurs during emulsification or the regulation of the particle diameter becomes difficult.
- the amount of introduced water as component (c) is important, and it is preferably varied depending on the ratio of the heavy oil (a) in the oil phase. That is, it is preferable that the ratio of the water to the heavy oil (a) is constant.
- a water-soluble polymer (d) and/or a polyhydric alcohol (g) as a stabilizer.
- the water-soluble polymer (d) having a molecular weight of 10,000 or more can be incorporated in an amount of 0.005 to 3 parts by weight, preferably 0.008 to 2 parts by weight, still preferably 0.01 to 0.5 parts by weight based on 100 parts by weight of the entire amount of the components (a), (b-2), (c) and (e-2) for the purpose of further improving the storage stability.
- the polyhydric alcohol (g) can be incorporated in an amount of 0.1 to 50 parts by weight, preferably 0.2 to 40 parts by weight, still preferably 0.3 to 30 parts by weight based on 100 parts by weight of the entire amount of the components (a), (b-2), (c) and (e-2) for the purpose of further improving the storage stability.
- the edible oil (e-2) can be incorporated by a method wherein the heavy oil (a) and the edible oil (e-2) are mixed or heat-mixed with each other before the production of an emulsion or a method wherein the edible oil (e-2) is added during the production of an emulsion. If necessary, the edible oil (e-2) may be added after the formation of an emulsion comprising a heavy oil (a) and water (c), followed by re-emulsification.
- the pH of the emulsion to which the edible oil (e-2) has been incorporated is in an acidic range.
- a hydroxide of an alkali metal, ammonia or an amine is suitable as the neutralizing agent.
- the neutralizing agent may be dissolved in water before the production of the emulsion or alternatively may be added during the production of the emulsion.
- the amount of addition of the neutralizing agent is preferably such that the resultant emulsion is neutral or weakly acidic or weakly alkaline.
- the neutralizing agent reacts with the edible oil (e-2) to form a soap.
- the neutralizing agent serves also as a saponifier. Therefore, the neutralizing agent is the neutralizing agent or saponifier (f) described above.
- the heavy oil emulsion fuel contains (b-1-2) a product obtained by reacting (e-2) an edible oil with (f) a neutralizing agent or saponifier.
- the heavy oil emulsion fuel comprises components (a), (c), (e-2) and (b-1-2), or components (a), (c) and (b-1-2), depending on the amount of the neutralizing agent or saponifier (f).
- the contents of the soot and dust and the nitrogen oxides present in the exhaust gases can be reduced through the following mechanism.
- Asphalts and bitumens as the heavy oil have higher residual carbon and nitrogen contents than those of gas oil, kerosine, fuel oil and other oils generally used as a fuel, so that when they are used as a fuel, an increase in the soot and dust and the nitrogen oxides is unavoidable.
- the edible oil (e-2) used in the present invention the calorific value in the combustion is substantially equal to that of the heavy oil, but no significant amount of residual carbon and residual nitrogen is present.
- the fuel NO x derived from nitrogen contained in the soot and dust and the fuel decreases with the incorporation of an increasing proportion of the edible oil (e-2) relative to the heavy oil (a).
- the proportion of incorporation of the edible oil (e-2) is increased, the burning off of the fuel is improved and the flame temperature rises, so that the amount of thermal NO x formed by the oxidation of nitrogen contained in the air is increased.
- the ratio of incorporation of the heavy oil (a) to the edible oil (e-2) is important.
- the high-concentration and low-viscosity emulsion of a heavy oil having a particular particle size distribution with respect to its oil phase is an epoch-making fuel which enables heavy oils, which have not been eFFectively utilized as an energy source in the art, such as bitumen and asphalt, to be used as a substitute fuel for heavy fuel oil.
- the fuel according to the present invention has a high heavy oil concentration and, at the same time, a low viscosity close to that of water, it has the great feature of enabling the boilers fired by heavy fuel oil commonly used in the art to be used without any modification.
- the heavy oil is in a fine particle form, the combustion efficiency is high and it is possible to reduce the amount of nitrogen oxides and sulfur oxides after combustion.
- An asphalt (specific gravity: 1.015, viscosity: 595 cP/100° C., softening point: 29° C., penetration: 370/25° C.) obtained from Arabian Light crude oil, a mixture of a nonionic surfactant (polyoxyethylene nonylphenyl ether; Emulgen 921 manufactured by Kao Corp.) with an anionic surfactant (potassium oleate soap; OS Soap manufactured by Kao Corp.) in a ratio of 1:1 and water were weighed in respective amounts necessary for one batch as specified in Table I-1. The oil phase component and the water phase component were mixed with each other at a temperature of 80° C.
- TK homomixer provided with a low-viscosity agitation blade
- the number of revolutions of the agitation blade was 10,000 or 5000 rpm, and the agitation time was 1 to 3 min.
- emulsions prepared using the number of revolutions of 10000 or 5000 rpm were mixed with each other (by manual mixing for 3 min) in a given mixing ratio as specified in Table I-2 to provide emulsion fuels according to the present invention. Thereafter, the emulsion fuels were allowed to stand in a thermostatic chamber at 20° C. for 24 hr and then subjected to a measurement of particle size, viscosity and storage stability. The results are given in Table I-2.
- Particle size The particle size was measured with a laser beam diffraction/scattering particle size distribution measuring device (LA700 manufactured by Horiba, Ltd.). The average particle diameter is a volumetric median diameter.
- Distribution constant (n) A-particle diameter corresponding to a cumulative oversize weight of 10% and one corresponding to a cumulative oversize weight of 90% were determined based on the results of the measurement of the particle size by fitting, and two relational expressions were obtained by substituting each of the particle diameters for the Rosin-Rammler distribution function, and the following calculation formula was derived from the two relational expressions and the distribution constant was determined by the following calculation formula: ##EQU1##
- Viscosity The viscosity was measured with a Brookfield viscometer (model BM) manufactured by Tokyo Keiki Co., Ltd. using rotors Nos. 3 and 4 at 60 rpm at 25° C. one min after the initiation of rotation.
- Solid concentration The weight of a cup made of aluminium (A mg) was measured precisely and then an emulsion fuel was poured into the cup. The total weight of the cup and the emulsion fuel (B mg) was measured precisely. The cup was allowed to stand in a drying box at 110° C. for 5 hr and then in a desiccator for 5 min to cool the cup to room temperature. The total weight of the cup and the residue of the emulsion fuel (C mg) was measured precisely and the solid concentration was calculated according to the following formula:
- An emulsion fuel was prepared by using the same asphalt as that of Example I-1, a nonionic surfactant (polyoxyethylene nonylphenyl ether, (a mixture of Emulgen 913 with Emulgen 920 (1/1), manufactured by Kao Corp.) and water on a line mixer (model PL-SL) manufactured by Tokushu Kika Kogyo Co., Ltd. More specifically, 800 g of the asphalt, 200 g of water and 10 g of the surfactant were weighed for one batch and premixed by manual stirring at a temperature of 80° C., and the mixture was emulsified on a line mixer.
- a nonionic surfactant polyoxyethylene nonylphenyl ether, (a mixture of Emulgen 913 with Emulgen 920 (1/1), manufactured by Kao Corp.) and water on a line mixer (model PL-SL) manufactured by Tokushu Kika Kogyo Co., Ltd. More specifically, 800 g of the asphalt, 200 g of water and 10
- Emulsification conditions are given in Table I-3, and various characteristics of the emulsion fuel as a fuel are given in Table I-4.
- the measurement conditions are the same as those of Example I-1.
- Orinoco tar (specific gravity: 0.99, viscosity: 23500 cSt/50° C.) produced around the Orinoco river in Venezuela was used as the heavy oil, and 750 g of Orinoco tar, 250 g of water, 10 g of a nonionic surfactant (polyoxyethylene nonylphenyl ether, a mixture of Emulgen 913 with Emulgen 920 (1/1), manufactured by Kao Corp.) and, as a water-soluble polymer for use in combination with the above-described components, polyvinyl alcohol (PVA220 manufactured by Kuraray Co., Ltd.), hydroxyethyl-cellulose (HEC SP-500 manufactured by Daicel Chemical Industries, Ltd.) or xanthan gum (Kelzan manufactured by Sankyo Co., Ltd.) in an amount specified in Table I-5 were used for one batch.
- PVA220 manufactured by Kuraray Co., Ltd.
- HEC SP-500 hydroxyethyl-cellulose
- Emulsion fuels were produced under the same emulsification conditions as those of Experiments Nos. 3 and 6 of Example I-2.
- the water-soluble polymer was dissolved in water together with the surfactant.
- Example I-6 Measurement conditions were the same as those of Example I-1, and the stability was measured 1 month and 6 months after the initiation of standing. The results are given in Table I-6.
- An emulsion fuel was produced from an asphalt (specific gravity: 1.015, viscosity: 595 cP/100° C., softening point: 29° C., penetration: 370/25° C.) obtained from Arabian Light crude oil by using, as an emulsifier, a TK homomixer (provided with a low-viscosity agitation blade) manufactured by Tokushu Kika Kogyo Co., Ltd. 225 g of the asphalt and 75 g of water were weighed for one batch and heated to 90° C.
- the emulsion fuels had a broad distribution having a distribution constant, n, of 1.8 or less.
- n distribution constant
- each of the emulsion fuels had a viscosity of 1000 cP or less, i.e., attained the object of the present invention.
- An emulsion fuel was produced in the same manner as that of Example II-1, except that Orinoco tar (specific gravity: 0.99, viscosity: 23500 cSt/50° C.) produced around the Orinoco river in Venezuela was used as the heavy oil, and, in addition, a nonionic surfactant (polyoxyethylene nonylphenyl ether; Emulgen 920 manufactured by Kao Corp.), and polyvinyl alcohol (PVA 220 manufactured by Kuraray Co., Ltd.), hydroxyethylcellulose (HECSP-500 manufactured by Daicel Chemical Industries, Ltd.), xanthan gum (Kelzan manufactured by Sansho Corp.) and polyethylene glycol (MW: 20000; manufactured by Wako Pure Chemical Industries Ltd.) as water-soluble polymers were also used.
- a nonionic surfactant polyoxyethylene nonylphenyl ether; Emulgen 920 manufactured by Kao Corp.
- PVA 220 polyvinyl alcohol
- HECSP-500
- asphalt obtained from Arabian Light crude oil (specific gravity: 1.015, viscosity: 595 cP/100° C, softening point: 29° C, penetration: 370/25° C)
- nonionic surfactant polyoxyethylene nonylphenyl ether (Emulgen 921 manufactured by Kao Corp.)
- anionic surfactant formaldehyde condensate of naphthalenesulfonic acid (Mighty 150 manufactured by Kao Corp.)
- carboxymethylcellulose (CMC1190 manufactured by Daicel Chemical Industries, Ltd.)
- potassium hydroxide (a reagent manufactured by Wako Pure Chemical Industries Ltd.)
- the asphalt, water, the surfactant, the fatty acid distillation bottom, the stabilizer and the neutralizing agent were each heated to 80° C. and fed into a reaction vessel (vessel diameter: 1.9 m) having a capacity of 5 m 3 , and the mixture was agitated at 80° C. for 60 min.
- a Pfaudler impeller was used as the agitation blade, and the diameter and number of revolutions of the blade were 1.1 m and 64 rpm, respectively.
- the mixture was emulsified by using a PL-SL line mixer manufactured by Tokushu Kika Kogyo Co., Ltd. according to a batch circulation system.
- the number of revolutions of the mixer and the emulsification time were 3600 rpm and 4 hr, respectively. After the completion of the emulsification, the system was cooled to 20° C. over a period of about 10 hr to provide an emulsion fuel for a combustion test.
- asphalt one obtained from Arabian Light crude oil (specific gravity: 1.015, viscosity: 595 cP/100° C., softening point: 29° C., penetration: 370/25° C.)
- nonionic surfactant polyoxyethylene nonylphenyl ether (Emulgen 921 manufactured by Kao Corp.)
- anionic surfactant formaldehyde condensate of naphthalenesulfonic acid (Mighty 150 manufactured by Kao Corp.)
- carboxymethylcellulose (CMC1190 manufactured by Daicel Chemical Industries, Ltd.)
- potassium hydroxide (a reagent manufactured by Wako Pure Chemical Industries Ltd.)
- Example III-2 About 4000 kg of an emulsion fuel was prepared in a similar manner to that of Example III-2, except that a recovered oil of an edible fat and oil is substituted for the fatty acid distillation bottom.
- the emulsion fuel produced was subjected to a combustion test in a similar manner to that of Example III-2.
Abstract
Description
R.sub.(D) =100 exp{-(D/D.sub.c).sup.n } (1)
R.sub.(D) =100 exp{-(D/D.sub.c).sup.n } (1)
R.sub.(D) =1OOexp{-(D/De).sup.n } (1)
RNHC.sub.3 H.sub.6 NH.sub.2 X' (6)
RNHC.sub.3 H.sub.6 NHC.sub.3 H.sub.6 NH.sub.2 X' (7)
R.sub.(D) =100 exp{-(D/D.sub.c).sup.n } (1)
R.sub.(D) =100 exp{-(D/D.sub.C).sup.n } (1)
log(R.sub.(D) /100)=-(D/D.sub.c).sup.n. log e
log.log(100/R.sub.(D))=n.log(D/D.sub.c)+log.log e
log.log(100/R.sub.(D))=n.logD-n.logD.sub.c +log.log e
log.log(100/90)=n.logD.sub.90 -n.logD.sub.c +log.log e
wherein D.sub.90 represents a particle diameter (μm) corresponding to a cumulative oversize weight of 90% (A)
log.log(100/10)=n.logD.sub.10 -n.logD.sub.c +log.log e wherein D.sub.10 represents a particle diameter (μm) corresponding to a cumulative oversize weight of 10% (B)
TABLE I-1 ______________________________________ Mixing and emulsification conditions No. of Surfac- revolutions Agitation Asphalt tant Water of blade time ______________________________________ Condition A 222 g 3.0 g 75 g 10000 rpm 3 min Condition B 246 g 3.0 g 51 g 5000 rpm 1 min Condition C 228 g 3.0 g 69 g 5000 rpm 1 min ______________________________________
TABLE I-2 __________________________________________________________________________ Results of measurement Emulsion prepara- Particle size distribution Stability tion Solid av. 100 μm 1 μm Distribu- Viscos- (after 1 month) condi- Mixing concn. particle or or tion ity upper lower Expt. No. tions ratio (%) diam. less less const. n (cP) layer layer __________________________________________________________________________ Comp. 1 A -- 78.8 2.8 μm 98.6% 15.4% 1.82 9800 gelation gelation Ex. 2 B -- 81.9 19.0 μm 95.3% 2.5% 1.89 7200 signifi- signifi- cant cant 3 C -- 83.8 32.9 μm 67.2% 0.3% 1.78 2700 somewhat gelation Inven- 4 A/B 50/50 80.5 11.2 μm 96.8% 6.8% 1.24 820 none none tion 5 A/C 50/50 81.2 16.7 μm 83.0% 5.1% 1.20 750 none none 6 A/B/C 33/34/33 80.8 12.9 μm 85.2% 4.3% 1.15 420 none none __________________________________________________________________________
TABLE I-3 __________________________________________________________________________ Emulsification conditions No. of revolutions Emulsification Expt. of mixer time on line No. (rpm) mixer (min) Emulsion withdrawal method __________________________________________________________________________ 1 4000 10 withdrawal in bulk after emulsification 2 6000 7 withdrawal in bulk after emulsification 3 8000 5 withdrawal in bulk after emulsification 4 4000 10 continuous withdrawal in portions during emulsification (100 cc/min) 5 6000 7 continuous withdrawal in portions during emulsification (140 cc/min) 6 8000 5 continuous withdrawal in portions during emulsification (200 cc/min) __________________________________________________________________________
TABLE I-4 __________________________________________________________________________ Results of measurement Particle size distribution Stability av. (after 1 month) particle 100 μm 1 μm distribution Viscosity upper lower Expt. No. diam. or less or less constant, n (cP) layer layer __________________________________________________________________________ Comp. 1 12.8 μm 98.1 7.7 1.64 7600 gelation gelation Ex. 2 12.1 μm 98.7 7.9 1.70 8300 gelation gelation 3 10.5 μm 99.2 8.0 1.88 9700 gelation gelation Inven- 4 14.3 μm 95.4 5.3 1.19 690 none none tion 5 13.8 μm 95.7 4.9 1.33 850 none none 6 11.4 μm 94.2 5.5 1.37 950 none none __________________________________________________________________________
TABLE I-5 __________________________________________________________________________ Emulsification conditions No. of Emulsifica- revolutions tion time Water-soluble polymer Expt. of mixer on line amt. of No. (rpm) mixer (min) Emulsion withdrawal method Name use (g) __________________________________________________________________________ Comp. 1 8000 5 withdrawal in bulk after -- -- Ex. emulsification 2 8000 5 withdrawal in bulk after PVA 220 1 emulsification Inven- 3 8000 5 continuous withdrawal in portions -- -- tion during emulsification (200 cc/min) 4 8000 5 continuous withdrawal in portions PVA 220 1 during emulsification (200 cc/min) 5 8000 5 continuous withdrawal in portions HEC SP-500 1 during emulsification (200 ec/min) 6 8000 5 continuous withdrawal in portions Kelzan ` 0.5 during emulsification (200 cc/min) __________________________________________________________________________
TABLE I-6 __________________________________________________________________________ Results of measurement Particle size distribution Stability Stability av. (after 1 month) (after 6 months) particle 100 μm 1 μm distribution Viscosity upper lower upper lower Expt. No. diam. or less or less constant, n (cP) layer layer layer layer __________________________________________________________________________ Comp. 1 8.5 μm 98.7 9.5 1.83 1550 somewhat none significant somewhat Ex. 2 7.6 μm 99.3 11.2 1.85 1820 none none none gelation Inven- 3 9.8 μm 96.2 7.0 1.31 310 somewhat none somewhat somewhat tion 4 8.3 μm 98.1 8.3 1.40 380 none none none none 5 8.0 μm 97.8 8.1 1.42 410 none none none none 6 7.7 μm 98.5 9.0 1.46 400 none none none none __________________________________________________________________________
TABLE II-1-A ______________________________________ Additives used Amt. of use Expt. No. Name of additives (g) ______________________________________ Comp. Ex. 1 mixed fatty acid soda soap 6.0 (Flake Marceilles manufactured by Kao Corp.) 2 oleic acid potash soap 6.0 (OS soap manufactured by Kao Corp.) 3 tallow fatty acid soda 6.0 soap (NS soap manufactured by Kao Corp) Invention 4 coconut oil/sodium 4.5/1.5 Ex. hydroxide 5 tallow/sodium hydroxide 4.5/1.5 6 palm oil/potassium 4.5/1.5 hydroxide 7 tall oil/potassium 4.5/1.5 hydroxide 8 oleic acid/potassium 4.5/1.5 hydroxide 9 stearic acid/potassium 4.5/1.5 hydroxide 10 stearic acid/ammonia 4.5/1.5 11 stearic acid/ 4.5/1.5 triethanolamine 12 abietic acid/potassium 4.5/1.5 hydroxide 13 naphthenic acid/potassium 4.5/1.5 hydroxide ______________________________________ Note: carboxylic acids and basic compounds are reagents manufactured by Wako Pure Chemical Industries Ltd.
TABLE II-1-B ______________________________________ Properties of fat and oil used m.p. sapon. iodine sp. gr. (°C.) value value ______________________________________ coconut oil 0.92 24 261 11 beef tallow 0.94 42 196 42 palm oil 0.93 38 203 50 tall oil 0.93 -- 199 -- ______________________________________
TABLE II-2 __________________________________________________________________________ Results of measurement Particle size distribution Stability distribu- (after 1 month) av. particle 100 μm or 1 μm or tion const. Viscosity upper lower Expt. No. diam. less less n (cP) layer layer __________________________________________________________________________ Comp. 1 6.7 μm 98.2% 12.0% 1.84 1740 none none Ex. 2 5.0 μm 98.3% 15.8% 1.90 2560 none none 3 8.5 μm 99.7% 13.2% 1.88 1980 none none Inven- 4 13.7 μm 96.3% 6.1% 1.29 390 none none tion 5 12.2 μm 96.7% 5.8% 1.25 370 none none Ex. 6 11.6 μm 94.9% 5.5% 1.27 380 none none 7 9.1 μm 98.1% 7.6% 1.19 380 none none 8 11.3 μm 95.4% 7.4% 1.52 650 none none 9 13.5 μm 96.8% 8.1% 1.59 700 none none 10 14.9 μm 95.3% 6.6% 1.52 590 none none 11 12.5 μm 95.1% 5.9% 1.55 550 none none 12 11.6 μm 94.5% 5.7% 1.52 560 none none 13 13.4 μm 96.0% 6.8% 1.51 470 none none __________________________________________________________________________
TABLE II-3 __________________________________________________________________________ Additives used Expt. No. Name of additives Amt. of use (g) __________________________________________________________________________ Comp. 1 tallow fatty acid soda soap 6.0 Ex. 2 mixed fatty acid soda soap 6.0 3 tallow fatty acid soda soap/nonionic surfactant 3.0/3.0 4 mixed fatty acid soda soap/nonionic surfactant 3.0/3.0 5 oleic acid potash soap/nonionic surfactant 3.0/3.0 6 tallow soda soap/nonionic surfactant/PVA220 3.0/3.0/0.3 Invention 7 coconut oil/sodium hydroxide 4.5/1.5 Ex. 8 tall oil/potassium hydroxide 4.5/1.5 9 coconut oil/sodium hydroxide/nonionic surfactant 2.3/0.8/3.0 10 beef tallow/sodium hydroxide/nonionic surfactnat 2.3/0.8/3.0 11 palm oil/potassium hydroxide/nonionic surfactant 2.3/0.8/3.0 12 tall oil/potassium hydroxide/nonionic surfactant 2.3/0.8/3.0 13 oleic acid/potassium hydroxide/nonionic surfactant 2.3/0.8/3.0 14 stearic acid/potassium hydroxide/nonionic surfactant 2.3/0.8/3.0 15 abietic acid/potassium hydroxide/nonionic surfactant 2.3/0.8/3.0 16 naphthenic acid/potassium hydroxide/nonionic surfactant 2.3/0.8/3.0 __________________________________________________________________________
TABLE II-4 __________________________________________________________________________ Additives used Expt. No. Name of additive Amt. of use (g) __________________________________________________________________________ Invention 17 beef tallow/sodium hydroxide/nonionic surfactant/PVA220 2.3/0.8/3.0/0.3 Ex. 18 beef tallow/sodium hydroxide/nonionic surfactant/HECSP-500 2.3/0.8/3.0/0.3 19 beef tallow/sodium hydroxide/nonionic surfactant/Kelzan 2.3/0.8/3.0/0.15 20 beef tallow/sodium hydroxide/nonionic surfactant/ 2.3/0.8/3.0/0.3 polyethylene glycol 21 coconut oil/sodium hydroxide/nonionic surfactant/PVA220 2.3/0.8/3.0/0.3 22 palm oil/potassium hydroxide/nonionic surafactant/PVA220 2.3/0.8/3.0/0.3 23 tall oil/potassium hydroxide/nonionic surfactant/PVA220 2.3/0.8/3.0/0.3 24 oleic acid/potassium hydroxide/nonionic surfactant/PVA220 2.3/0.8/3.0/0.3 25 stearic acid/potassium hydroxide/ 2.3/0.8/3.0/0.3 nonionic surfactant/PVA220 26 abietic acid/potassium hydroxide/ 2.3/0.8/3.0/0.3 nonionic surfactant/PVA220 27 napthenic acid/potassium hydroxide/ 2.3/0.8/3.0/0.3 nonionic surfactant/PVA220 __________________________________________________________________________
TABLE II-5 __________________________________________________________________________ Results of measurement Particle size distribution Stability Stability av. 100 μm 1 μm distribu- Viscos- (after 1 month) (after 6 months) particle or or tion const. ity upper lower upper lower Expt. No. diam. less less n (cP) layer layer layer layer __________________________________________________________________________ Comp. 1 7.5 μm 98.0 11.0 1.83 1240 none none significant somewhat Ex. 2 6.8 μm 98.7 10.8 1.90 1220 none none significant somewhat 3 4.9 μm 99.2 12.7 1,89 1370 none none somewhat none 4 4.6 μm 99.5 13.3 1.92 1450 none none somewhat none 5 3.8 μm 99.3 15.8 1.90 1380 none none somewhat none 6 3.3 μm 99.6 17.1 1.97 2310 none none none gelation Inven- 7 10.3 μm 97.0 8.7 1.15 260 none none somewhat somewhat tion 8 11.5 μm 96.9 8.5 1.13 240 none none somewhat somewhat Ex. 9 8.8 μm 97.2 9.2 1.27 350 none none somewhat none 10 9.0 μm 96.8 9.0 1.27 370 none none somewhat none 11 8.9 μm 98.5 9.7 1.25 330 none none somewhat none 12 8.2 μm 99.0 10.3 1.18 280 none none somewhat none 13 7.7 μm 98.0 12.5 1.47 520 none none somewhat none 14 7.5 μm 97.8 11.0 1.40 580 none none somewhat none 15 7.8 μm 98.1 12.2 1.39 490 none none somewhat none 16 6.9 μm 98.2 11.5 1.49 510 none none somewhat none __________________________________________________________________________
TABLE II-6 __________________________________________________________________________ Results of measurement Particle size distribution Stability Stability av. 100 μm 1 μm distribu- Viscos- (after 1 month) (after 6 months) particle or or tion const. ity upper lower upper lower Expt. No. diam. less less n (cP) layer layer layer layer __________________________________________________________________________ Invention 17 7.5 μm 99.0 12.0 1.33 650 none none none none Ex. 18 6.9 μm 99.1 11.7 1.29 670 none none none none 19 7.2 μm 98.6 12.5 1.35 790 none none none none 20 6.8 μm 98.8 12.7 1.38 570 none none none none 21 7.8 μm 98.0 11.4 1.42 570 none none none none 22 7.5 μm 99.2 12.5 1.48 590 none none none none 23 7.0 μm 98.8 11.5 1.45 630 none none none none 24 6.2 μm 98.6 12.7 1.55 780 none none none none 25 6.9 μm 99.0 13.4 1.49 750 none none none none 26 5.9 μm 99.3 12.2 1.50 750 none none none none 27 6.6 μm 99.6 14.0 1.51 770 none none none none __________________________________________________________________________
TABLE III-1 __________________________________________________________________________ Compositions Fatty acid Nonionic Anionic distillation Neutralizing Expt. Asphalt Water surfactant surfactant bottom Stabilizer agent No. (g) (g) (g) (g) (g) (g) (g) __________________________________________________________________________ Comp. 1 210 90 1.5 1.5 -- -- -- Ex. Inven- 2 207 90 1.5 1.5 3.0 -- -- tion 3 180 90 1.5 1.5 30.0 -- -- 4 207 90 1.5 1.5 3.0 0.3 -- 5 180 90 1.5 1.5 30.0 0.3 -- 6 180 90 1.5 1.5 30.0 -- 6.0 7 180 90 1.5 1.5 30.0 0.3 6.0 __________________________________________________________________________
TABLE III-2 __________________________________________________________________________ Results of measurement Av. particle Expt. diam. Viscosity Stability No. (μm) (cP) skinning water separation sedimentation __________________________________________________________________________ Comp. 1 7.5 830 none none none Ex. Invention 2 8.0 810 none none none Ex. 3 7.8 960 none none none 4 7.2 930 none none none 5 7.1 990 none none none 6 8.3 650 none none none 7 7.7 840 none none none __________________________________________________________________________
TABLE III-3 __________________________________________________________________________ Results of combustion test Exhaust gas Av. particle content of content of nitrogen Expt. diam. Viscosity oxygen soot and dust oxides No. (μm) (cP) (%) (g/m.sup.3) (ppm) __________________________________________________________________________ Comp. 1 13.7 790 4.0 0.16 254 Ex. Invention 2 14.5 700 4.1 0.11 226 Ex. 3 14.5 850 3.9 0.09 210 4 13.1 860 3.9 0.10 235 5 13.0 940 4.0 0.08 217 6 15.9 670 4.1 0.07 216 7 13.6 820 3.9 0.07 203 __________________________________________________________________________
TABLE IV-1 __________________________________________________________________________ Compositions Recovered oil Nonionic Anionic of edible fat Neutralizing Expt. Asphalt Water surfactant surfactant and oil Stabilizer agent No. (g) (g) (g) (g) (g) (g) (g) __________________________________________________________________________ Comp. 1 210 90 1.5 1.5 -- -- -- Ex. 2 -- 90 1.5 1.5 210 -- -- Invention 3 195 90 1.5 1.5 15 -- -- Ex. 4 15 90 1.5 1.5 195 -- -- 5 105 90 1.5 1.5 105 -- -- 6 105 90 1.5 1.5 105 0.3 -- 7 105 90 1.5 1.5 105 -- 6.0 8 105 90 1.5 1.5 105 0.3 6.0 __________________________________________________________________________
TABLE IV-2 __________________________________________________________________________ Results of measurement Av. particle Expt. diam. Viscosity Stability No. (μ) (cP) skinning water separation sedimentation __________________________________________________________________________ Comp. 1 7.5 830 none significant somewhat Ex. 2 8.3 230 none significant none Invention 3 7.8 650 none none none Ex. 4 8.0 380 none none none 5 7.5 450 none none none 6 7.0 530 none none none 7 8.7 380 none none none 8 7.8 400 none none none __________________________________________________________________________
TABLE IV-3 __________________________________________________________________________ Results of combustion test Exhaust gas Av. particle content of soot content of nitrogen Expt. diam. Viscosity oxygen and dust oxides No. (μ) (cP) (%) (g/m.sup.3) (ppm) __________________________________________________________________________ Comp. 1 13.7 790 4.0 0.16 254 Ex. 2 15.9 180 4.0 0.05 270 Invention 3 14.1 450 4.0 0.12 237 Ex. 4 15.4 230 4.1 0.08 230 5 14.7 330 4.0 0.10 215 6 13.8 370 3.9 0.09 213 7 16.4 280 4.1 0.11 211 8 14.0 340 3.9 0.10 209 __________________________________________________________________________
Claims (36)
R.sub.(D) =100 exp{-(D/D.sub.c).sup.n } (1)
R.sub.(D) =100exp{-(D/De).sup.n } (1)
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JP4254798A JP3069674B2 (en) | 1992-09-24 | 1992-09-24 | Method for producing heavy oil emulsion fuel |
JP4-254798 | 1992-09-24 |
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